Computation of Molecular Electron Affinities Using an Ensemble Density Functional Theory Method

The computation of electron attachment energies (electron affinities) was implemented in connection with an ensemble density functional theory method, the state-interaction state-averaged spin-restricted ensemble-referenced Kohn–Sham (SI-SA-REKS or SSR) method. With the use of the extended Koopmans’ theorem, the electron affinities and the respective Dyson orbitals are obtained directly for the neutral molecule, thus avoiding the necessity to compute the ionized system. Together with the EKT-SSR (extended Koopmans’ theorem-SSR) method for ionization potentials, which was developed earlier, EKT-SSR for electron affinities completes the implementation of the EKT-SSR formalism, which can now be used for obtaining electron detachment as well as the electron attachment energies of molecules in the ground and excited electronic states. The extended EKT-SSR method was tested in the calculation of several closed-shell molecules. For the molecules in the ground states, the EKT-SSR energies of Dyson’s orbitals are virtually identical to the energies of the unoccupied orbitals in the usual single-reference spin-restricted Kohn–Sham calculations. For the molecules in the excited states, EKT-SSR predicts an increase of the most positive electron affinity by approximately the amount of the vertical excitation energy. The electron affinities of a number of diradicals were calculated with EKT-SSR and compared with the available experimental data. With the use of a standard density functional (BH&HLYP), the EKT-SSR electron affinities deviate on average by ca. 0.2 eV from the experimental data. It is expected that the agreement with the experiment can be improved by designing density functionals parametrized for ionization energies

Structural or population dynamics: what is revealed by the time-resolved photoelectron spectroscopy of 1,3-cyclohexadiene? A study with an ensemble density functional theory method

Time-resolved photoelectron spectra during the photochemical ring-opening reaction of 1,3-cyclohexadiene (CHD) are modeled by an ensemble density functional theory (eDFT) method. The computational methodology employed in this work is capable of correctly describing the multi-reference effects arising in the ground and excited electronic states of molecules, which is important for the correct description of the ring-opening reaction of CHD. The geometries of molecular species along the non-adiabatic molecular dynamics (NAMD) trajectories reported in a previous study of the CHD photochemical ring-opening were used in this work to calculate the ionization energies and the respective Dyson orbitals for all possible ionization channels. The obtained theoretical time-resolved spectra display decay characteristics in a reasonable agreement with the experimental observations; i.e., the decay (and rise) of the most mechanistically significant signals occurs on the timescale of 100–150 fs. This is very different from the excited state population decay characteristics (τ _(S1) = 234 ± 8 fs) obtained in the previous NAMD study. The difference between the population decay and the decay of the photoelectron signal intensity is traced back to the geometric transformation that the molecule undergoes during the photoreaction. This demonstrates the importance of including the geometric information in interpretation of the experimental observations

Computation of Molecular Electron Affinities Using an Ensemble Density Functional Theory Method

The computation of electron attachment energies (electron affinities) was implemented in connection with an ensemble density functional theory method, the state-interaction state-averaged spin-restricted ensemble-referenced Kohn–Sham (SI-SA-REKS or SSR) method. With the use of the extended Koopmans’ theorem, the electron affinities and the respective Dyson orbitals are obtained directly for the neutral molecule, thus avoiding the necessity to compute the ionized system. Together with the EKT-SSR (extended Koopmans’ theorem-SSR) method for ionization potentials, which was developed earlier, EKT-SSR for electron affinities completes the implementation of the EKT-SSR formalism, which can now be used for obtaining electron detachment as well as the electron attachment energies of molecules in the ground and excited electronic states. The extended EKT-SSR method was tested in the calculation of several closed-shell molecules. For the molecules in the ground states, the EKT-SSR energies of Dyson’s orbitals are virtually identical to the energies of the unoccupied orbitals in the usual single-reference spin-restricted Kohn–Sham calculations. For the molecules in the excited states, EKT-SSR predicts an increase of the most positive electron affinity by approximately the amount of the vertical excitation energy. The electron affinities of a number of diradicals were calculated with EKT-SSR and compared with the available experimental data. With the use of a standard density functional (BH&HLYP), the EKT-SSR electron affinities deviate on average by ca. 0.2 eV from the experimental data. It is expected that the agreement with the experiment can be improved by designing density functionals parametrized for ionization energies

Structural or population dynamics: what is revealed by the time-resolved photoelectron spectroscopy of 1,3-cyclohexadiene? A study with an ensemble density functional theory method

Time-resolved photoelectron spectra during the photochemical ring-opening reaction of 1,3-cyclohexadiene (CHD) are modeled by an ensemble density functional theory (eDFT) method. The computational methodology employed in this work is capable of correctly describing the multi-reference effects arising in the ground and excited electronic states of molecules, which is important for the correct description of the ring-opening reaction of CHD. The geometries of molecular species along the non-adiabatic molecular dynamics (NAMD) trajectories reported in a previous study of the CHD photochemical ring-opening were used in this work to calculate the ionization energies and the respective Dyson orbitals for all possible ionization channels. The obtained theoretical time-resolved spectra display decay characteristics in a reasonable agreement with the experimental observations; i.e., the decay (and rise) of the most mechanistically significant signals occurs on the timescale of 100–150 fs. This is very different from the excited state population decay characteristics (τ _(S1) = 234 ± 8 fs) obtained in the previous NAMD study. The difference between the population decay and the decay of the photoelectron signal intensity is traced back to the geometric transformation that the molecule undergoes during the photoreaction. This demonstrates the importance of including the geometric information in interpretation of the experimental observations

THE FIRST-YEAR EXPERIENCE INCORPORATING THE ORGANIZATIONAL DEVELOPMENT APPROACH AT KOBE TOKIWA UNIVERSITY

In Japan, the first-year experience that rapidly gained attention at the beginning of the twenty-first century was clearly positioned in 2008 as formal undergraduate educational programs (The Central Council for Education, 2008). The term “first-year experience” is defined as a “comprehensive educational program primarily created for freshmen” to promote their smooth transition from high school to university and to create successful academic and social experiences at university (The Central Council for Education, 2008). Thus, the first-year experience is a specific program with activities implemented by diverse universities to fit the unique needs of their first-year university students (Tachi, 2008). One important issue of the first-year experience within the undergraduate program has been identifying ways to guarantee the quality of education. Kobe Tokiwa University’s four departments (medical technology, nursing, child education, and dental hygiene) require students to gain strong abilities to collaborate and cooperate in teams to be responsible for future team medical care or a school as a team. Therefore, in 2018, the university implemented a first-year experience program that incorporated the organizational development approach instead of the conventional human resource development approach. This article shares our experiences using a first-year experience program that incorporates the organizational development approach, and we discuss the potential of this approach for the first-year experience. To estimate the effectiveness of organizational development approach in FYE, we analyzed and compared the interim data that were reported on students in 2017 and 2018 using a text mining method. By introducing this “Organizational Development” approach into the students’ first-year educational curriculum, results suggest that it is possible to “deepen self-understanding” and “cooperate in self-understanding of others” at an early stage of a student’s enrollment. It is thought that this approach could become another effective method for universities to use for training professional persons as interpersonal aid workers

Analytic Gradient for Density Functional Theory Based on the Fragment Molecular Orbital Method

The equations for the response terms for the fragment molecular orbital (FMO) method interfaced with the density functional theory (DFT) gradient are derived and implemented. Compared to the previous FMO–DFT gradient, which lacks response terms, the FMO–DFT analytic gradient has improved accuracy for a variety of functionals, when compared to numerical gradients. The FMO–DFT gradient agrees with the fully ab initio DFT gradient in which no fragmentation is performed, while reducing the nonlinear scaling associated with standard DFT. Solving for the response terms requires the solution of the coupled perturbed Kohn–Sham (CPKS) equations, where the CPKS equations are solved through a decoupled Z-vector procedure called the self-consistent Z-vector method. FMO–DFT is a nonvariational method and the FMO–DFT gradient is unique compared to standard DFT gradients in that the FMO–DFT gradient requires terms from both DFT and time-dependent density functional theory (TDDFT) theories